CN101077422A - Medical adhesive and medical adhesive tape or sheet - Google Patents
Medical adhesive and medical adhesive tape or sheet Download PDFInfo
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- CN101077422A CN101077422A CNA2007101097235A CN200710109723A CN101077422A CN 101077422 A CN101077422 A CN 101077422A CN A2007101097235 A CNA2007101097235 A CN A2007101097235A CN 200710109723 A CN200710109723 A CN 200710109723A CN 101077422 A CN101077422 A CN 101077422A
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- adhesive
- medical adhesive
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/44—Medicaments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Abstract
The present invention provides a medical adhesive and a medical adhesive tape or sheet superior in the fixing performance, particularly perspiration-resistant fixing, which shows low skin irritation and suitable adhesive strength. The present invention provides a medical adhesive containing a water-dispersed copolymer obtained by copolymerizing 100 parts by weight of a monomer mixture containing (meth)acrylic acid alkyl ester and 0.005-2 parts by weight of a silane monomer copolymerizable with the ester, and an organic liquid component compatible with the copolymer; a medical adhesive containing a water-dispersed copolymer obtained by copolymerizing a monomer mixture containing (meth)acrylic acid alkyl ester and a silane monomer copolymerizable with the ester, and an organic liquid component compatible with the copolymer, wherein the gel fraction after crosslinking of the copolymer is 40-80 wt%, and the weight average molecular weight of a sol component after crosslinking is not less than 300000; and a medical adhesive tape or sheet having the medical adhesive at least on one surface of a support.
Description
Technical field
The present invention relates to a kind of medical adhesive that is applied to fields such as medical and health.The present invention also relates to a kind of medical adhesive dressing band or sheet adhesive as adhering bandage, surgical tape, first aid adhesive tape, large scale adhesive tape, stretch tight bundle material, paste (cataplasm) etc.
Background technology
Be fixed to the purpose of skin for the Transdermal absorption of the protection of skin injury, medicine and with gauze or pipe etc., tradition has been developed medical adhesive dressing band (adhesivetape) and the sheet adhesive (adhesive sheet) of using multiple medical adhesive.Because medical adhesive dressing band and sheet adhesive major part are adhered on the skin, so need adhesivity be arranged, further say skin, need to have the pipe etc. of repulsion to be fixed to ability on the skin.Simultaneously, require them not cause the pain or the infringement of skin, as peel off horny layer etc.
As the adhesive of the adhesive layer that is used for medical adhesive dressing band or sheet adhesive, the general adhesive of forming by (methyl) acrylate polymer that uses, this polymer has adhesivity and poisture-penetrability preferably, and less to the chemical stimulation of skin.
But,, use the adhesive tape of this adhesive or sheet adhesive when skin is peeled off, can cause pain or infringement to the horny layer and the epidermis of skin because the adhesive strength of the adhesive that is made of (methyl) acrylate polymer is too big.
Especially, when adhesive tape or sheet adhesive repeated application during, can cause that with the skin lesion of bleeding, this causes serious problem in identical position.
In order to reduce this physical stimulation to skin, someone (for example, referring to JP-A-6-23029 and JP-A-6-319793) a kind of gel (gel) adhesive proposed, its by in (methyl) acrylate polymer, add in a large number can with the organic liquid composition of polymer-compatible, and make polymer carry out crosslinking Treatment and obtain.
This gel adhesive can reduce and be dispersed in the stress that acts on skin surface when peeling off, simultaneously the high adhesivity that keeps (methyl) acrylate polymer to have.Therefore, because they less cause the physical stimulation to skin, and peel off horny layer etc. hardly, this adhesive can be used in percutaneous plaster (transdermal patch) and medical surgical adhesive tape.
Summary of the invention
By being laminated to adhesive tape or the sheet adhesive that obtains on the carrier as disclosed gel adhesive in above-mentioned arbitrary references, only deficiently medical pipe is fixed on the skin, and the absorption of perspiration fixed performance that presents remarkable deterioration sometimes is especially when summer, perspire increased.
The medical adhesive that contains disclosed adhesive in above-mentioned arbitrary references, major part are preparations in organic solvent such as ethyl acetate etc., and present case is worthless fully for environmental health.
The inventor furthers investigate, trial addresses the above problem, and find and a kind ofly can be effectively be fixed in the medical adhesive of skin having the medical apparatus of repulsion such as medical pipe etc., this medical adhesive has absorption of perspiration fixed performance preferably, it can obtain by the organic liquid component of dissolving in water-dispersed copolymer, and this water-dispersed copolymer is by obtaining with specific ratio (rate) copolymerization silane monomer and the monomer mixture that contains (methyl) alkyl acrylate.
The inventor has carried out further further investigation, and find a kind of medical adhesive that contains water-dispersed copolymer and organic liquid composition that can be compatible with water-dispersed copolymer, this water-dispersed copolymer can obtain with the monomer mixture that contains (methyl) alkyl acrylate with the silane monomer of (methyl) alkyl acrylate copolymer by copolymerization, this medical adhesive has specific physical characteristic, can be effectively be fixed in skin with having the medical apparatus of repulsion such as medical pipe etc., and have absorption of perspiration fixed performance preferably, so just finished the present invention.
That is, the invention provides following content:
[1] a kind of medical adhesive that contains water-dispersed copolymer and organic liquid composition that can be compatible with water-dispersed copolymer, this water-dispersed copolymer can obtain with the silane monomer of (methyl) alkyl acrylate copolymer by monomer mixture and the 0.005-2 weight portion that copolymer-1 00 weight portion contains (methyl) alkyl acrylate.
[2] medical adhesive of above-mentioned [1], wherein, contain in the monomer mixture of (methyl) alkyl acrylate at 100 weight portions, the monomer mixture that contains (methyl) alkyl acrylate comprise the 0.1-10 weight portion can with the carboxylic monomer of (methyl) alkyl acrylate copolymer.
[3] medical adhesive of above-mentioned [1] or [2], the gel percentage rate (gel fraction) of wherein crosslinked back water-dispersed copolymer is 30-80wt%.
[4] a kind of medical adhesive dressing band or sheet adhesive contain the arbitrary medical adhesive in above-mentioned [1]-[3] on the one side at least of carrier.
[5] a kind of medical adhesive, it contains water-dispersed copolymer and organic liquid composition that can be compatible with water-dispersed copolymer, this water-dispersed copolymer contains the monomer mixture of (methyl) alkyl acrylate by copolymerization and can obtain with the silane monomer of (methyl) alkyl acrylate copolymer
The gel percentage rate of wherein crosslinked back water-dispersed copolymer is 40-80wt%, and the weight average molecular weight of colloidal sol (sol) composition of crosslinked back water-dispersed copolymer is not less than 300000.
[6] medical adhesive of above-mentioned [5], the no more than 30wt% of gel percentage rate of wherein crosslinked preceding water-dispersed copolymer.
[7] medical adhesive of above-mentioned [5], the weight-average molecular weight/number-average molecular weight of the colloidal sol composition of wherein crosslinked back water-dispersed copolymer is 3-7.
[8] arbitrary medical adhesive in above-mentioned [5]-[7], wherein, contain in the monomer mixture of (methyl) alkyl acrylate at 100 weight portions, the monomer mixture that contains (methyl) alkyl acrylate comprise the 0.1-10 weight portion can with the carboxylic monomer of (methyl) alkyl acrylate copolymer, and water-dispersed copolymer obtains by the monomer mixture that copolymerization 0.005-2 weight portion can contain (methyl) alkyl acrylate with the silane monomer and 100 weight portions of (methyl) alkyl acrylate copolymer.
[9] a kind of medical adhesive dressing band or sheet adhesive contain the arbitrary medical adhesive in above-mentioned [5]-[8] on the one side at least of carrier.
Medical adhesive of the present invention has suitable adhesivity, good fixed performance and absorption of perspiration fixed performance simultaneously to skin, and, even when being used for medical adhesive dressing band or sheet adhesive etc., will peel off them and the physical stimulation that causes is suppressed to low-level from adherend.In addition because medical adhesive of the present invention in it is produced not with an organic solvent, so be preferable for environmental health.
The specific embodiment
The present invention relates to a kind of medical adhesive that contains water-dispersed copolymer and organic liquid composition that can be compatible with water-dispersed copolymer, this water-dispersed copolymer contains the monomer mixture of (methyl) alkyl acrylate by copolymerization and can obtain with the silane monomer of (methyl) alkyl acrylate copolymer, and provides:
(1) a kind of medical adhesive that contains water-dispersed copolymer and organic liquid composition that can be compatible with water-dispersed copolymer, this water-dispersed copolymer can obtain (claiming sometimes that hereinafter this medical adhesive is first medical adhesive of the present invention) with the silane monomer of (methyl) alkyl acrylate copolymer by monomer mixture and the 0.005-2 weight portion that copolymer-1 00 weight portion contains (methyl) alkyl acrylate, and
(2) a kind of medical adhesive that contains water-dispersed copolymer and organic liquid composition that can be compatible with water-dispersed copolymer, this water-dispersed copolymer contains the monomer mixture of (methyl) alkyl acrylate by copolymerization and can obtain with the silane monomer of (methyl) alkyl acrylate copolymer
The gel percentage rate of wherein crosslinked back water-dispersed copolymer is 40-80wt%, and the weight average molecular weight of the colloidal sol composition of crosslinked back water-dispersed copolymer was not less than for 300000 (claiming sometimes that hereinafter this medical adhesive is second medical adhesive of the present invention).
In this manual, medical adhesive of the present invention comprises above-mentioned first and second medical adhesives of the present invention.
Medical adhesive of the present invention is crosslinked by silane monomer.
Though be used for the monomer mixture that contains (methyl) alkyl acrylate of medical adhesive of the present invention is to comprise the monomer mixture of (methyl) alkyl acrylate (preferred 50-100wt%) as main component, but about this point, following silane monomer is not included in the monomer mixture.
For (methyl) alkyl acrylate, used (methyl) alkyl acrylate, wherein moieties be have be no less than 1, preferred no more than 15, the more preferably straight or branched alkyl of 1-9 carbon atom.Particularly, for example, can use (methyl) alkyl acrylate, such as (methyl) acrylic acid methyl ester. with straight or branched alkyl group, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) acrylic acid n-octyl, (methyl) Isooctyl acrylate monomer, 2-ethylhexyl (methyl) acrylate, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, undecyl (methyl) acrylate, tridecyl (methyl) acrylate etc.These can use separately or two or more are used in combination.Especially, preferred acrylic acid n-octyl, Isooctyl acrylate monomer, 2-ethylhexyl acrylate, acrylic acid ester in the positive ninth of the ten Heavenly Stems, acrylic acid ester in the different ninth of the ten Heavenly Stems, methyl methacrylate, ethyl methacrylate and n-BMA.
Be used for can being not particularly limited of medical adhesive of the present invention, so long as contain silicon atom and can get final product with the polymerisable chemical compound of (methyl) alkyl acrylate copolymer with the silane monomer of (methyl) alkyl acrylate copolymer.From having copolymerized ability preferably, preferably has the silane compound of (methyl) acryloyl group, such as (methyl) acryloyloxyalkyl silane derivative etc. with (methyl) alkyl acrylate.The example of silane monomer chemical compound comprises 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group methyl dimethoxysilane, 3-(methyl) acryloxy propyl group methyldiethoxysilane etc.These silane monomers can use separately or two or more are used in combination.Especially, preferred 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane and 3-acryloxy propyl trimethoxy silicane.
Except that foregoing, for silane monomer, for example, can use vinyltrimethoxy silane, VTES, 4-vinyl butyl trimethoxy silane, 4-vinyl butyl triethoxysilane, 8-vinyl octyl group trimethoxy silane, 8-vinyl octyltri-ethoxysilane, 10-methacryloxy decyl trimethoxy silane, 10-acryloxy decyl trimethoxy silane, 10-methacryloxy decyl triethoxysilane, 10-acryloxy decyl triethoxysilane etc.
Contain the monomer mixture of (methyl) alkyl acrylate by 100 weight portions, with 0.005-2 weight portion, preferred 0.005-1 weight portion, more preferably the quantity copolymerization of 0.01-0.4 weight portion constitutes the silane monomer of first medical adhesive of the present invention.When the copolymerization amount of silane monomer surpasses 2 weight portions, may not obtain sufficient fixed performance, and when it is less than 0.005 weight portion, because not enough polymer strength can easily make the cohesive force reduction, and may produce problem such as adhesive residue.
In second medical adhesive of the present invention, above-mentioned silane monomer, with preferred 0.005-2 weight portion, more preferably 0.005-1 weight portion, the quantity of especially preferred 0.01-0.4 weight portion, contain the monomer mixture of (methyl) alkyl acrylate with respect to 100 weight portions, carry out copolymerization.
When the copolymerization amount of silane monomer surpasses 2 weight portions, may not obtain sufficient fixed performance, and when it is less than 0.005 weight portion, because not enough polymer strength can easily make the cohesive force reduction, and may produce problem such as adhesive residue.
In medical adhesive of the present invention, by silane monomer and the monomer mixture copolymerization that contains (methyl) alkyl acrylate, the silane compound that will be crosslink sites is that homogeneous exists in the molecule of gained copolymer.Therefore, though medical adhesive of the present invention is water-decentralized, water-particulate inside of dispersion agent stick and outside are that homogeneous is crosslinked.As a result, obtained cohesive force preferably, and thereby realized simultaneously by adding low skin irritation that the organic liquid composition obtains and fixed performance and absorption of perspiration fixed performance preferably.
In medical adhesive of the present invention, from silane monomer hydrolysis and the adhesivity adjusting aspect that is realized, preferably, above-mentioned containing (methyl) alkyl acrylate monomer mixture should contain can with the carboxylic monomer of (methyl) alkyl acrylate copolymer.
From silane monomer hydrolysis and the adhesivity adjusting aspect that realized, in containing the monomer mixture of (methyl) alkyl acrylate, 100 weight portions contain proportional be preferred 0.1-10 weight portion, more preferably 0.5-8 weight portion, the more preferably above-mentioned carboxylic monomer of 1-6 weight portion also.
When carboxylic monomeric amount is lower than 0.1 weight portion, not hydrolysis of silane monomer and do not promote cross-linking reaction.As a result, insoluble content becomes littler, and adhesive often keeps when peeling off.When this amount surpasses 10 weight portions, following problems occurs: solution viscosity becomes big in the polymerization process, and it is difficult that the production of adhesive becomes.
Especially the restriction can with the carboxylic monomer of (methyl) alkyl acrylate copolymer, as long as its be in its structure, have carboxylic group and can with the polymerisable chemical compound of (methyl) alkyl acrylate copolymer.For example, can use (methyl) acrylic acid, itaconic acid, maleic acid, maleic anhydride, 2-methacryloxyethyl succinic acid etc.Especially, preferred acrylic acid and 2-methacryloxyethyl succinic acid.
In case of necessity, by copolymerization except silane monomer and carboxylic monomer can with the monomer of (methyl) alkyl acrylate copolymer, can obtain to constitute the water-dispersed copolymer of medical adhesive of the present invention.When medical adhesive of the present invention is used for medical adhesive dressing band or sheet adhesive etc., can use the cohesive force that can adjust adhesive layer with the monomer of (methyl) alkyl acrylate copolymer except silane monomer and carboxylic monomer, this has improved compatibility with the organic liquid composition etc.Its use amount can freely be determined by the content that replaces part (methyl) alkyl acrylate according to purpose.
Except silane monomer and carboxylic monomer, can comprise the monomer that contains sulfonyl (sulfoxyl), as styrene sulfonic acid, allyl sulphonic acid, (methyl) acrylic acid sulphur propyl ester, (methyl) acryloxy LOMAR PWA EINECS 246-676-2, acrylamide methyl propane sulfonic acid etc. with the monomeric example of (methyl) alkyl acrylate copolymer; The monomer of hydroxyl is as (methyl) hydroxyethyl acrylate, (methyl) acrylic acid hydroxypropyl ester etc.; The monomer of phosphinylidyne-containing amine group is as (methyl) acrylamide, dimethyl (methyl) acrylamide, N-butyl acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide etc.; (methyl) acrylic acid alkyl aminoalkyl ester is as (methyl) acrylic-amino ethyl ester, (methyl) acrylic acid dimethyl aminoethyl ester, (methyl) acrylic acid tert-butyl group amino-ethyl ester etc.; (methyl) alkoxyalkyl acrylate is as (methyl) acrylic acid methoxy ethyl ester, (methyl) acrylic acid ethoxyethyl group ester etc.; (methyl) acrylate that contains alkoxyl (or the ehter bond on the side chain) is as (methyl) acrylic acid methoxyl group glycol ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid methoxyl group glycol ester, (methyl) acrylic acid methoxyl group diethylene glycol ester, (methyl) acrylic acid methoxy poly (ethylene glycol) ester, (methyl) acrylic acid methoxyl group polypropylene glycol ester etc.; Vinyl monomer, as (methyl) acrylonitrile, vinylacetate, propionate, N-vinyl-2-Pyrrolidone, methyl ethylene ketopyrrolidine, vinylpyridine, vinyl piperidines, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, caprolactam, vinyl azoles, vinyl morpholine etc., also can mention analog.They can use separately or two or more are used in combination.Especially, the monomer of preferred hydroxyl and (methyl) alkoxyalkyl acrylate.
Water-the dispersed copolymer that constitutes medical adhesive of the present invention is made by the water-dispersion of the copolymer that the copolymerization by aforementioned monomer obtains, and can carry out water-dispersion that conventional emulsion polymerization makes conduct (methyl) alkyl acrylate copolymer by for example making the monomer mixture that contains (methyl) alkyl acrylate and the mixture of silane monomer.
Being used for water-dispersed copolymer generally is the about 50-400 weight portion of per 100 weight parts waters-dispersed copolymer solids content as the amount of the water of dispersion medium.
About polymerization, can adopt conventional integral body (en bloc) polymerization, continue to splash into polymerization, the part mode splashes into polymerization etc., and polymerization temperature is, for example, and approximately 20-100 ℃, preferably approximately 20-80 ℃.Though polymerization time is different with the difference of polymerization, general about is 3-24 hour.
The example that is used for polymeric polymerization initiator includes but not limited to, azo initiator, as 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2-methyl-prop amidine) dithionate (2,2 '-azobis (2-methylpropionamidine) disulfate), 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two [2-(5-methyl-2-imidazoline-2-yl) propane] dihydrochloride, 2,2 '-azo two (N, 2,2 N '-dimethylene isobutyl amidine), '-azo two [N-(2-carboxyethyl)-2-methyl-prop amidine] hydrate etc.; Persulfate is as potassium peroxydisulfate, Ammonium persulfate. etc.; Peroxide initiator is as benzoyl peroxide, tert-butyl hydrogen peroxide, hydrogen peroxide etc.; The ethane initiator that replaces is as the ethane of phenyl-replacement etc.; The fragrance carbonyl compound; Redox initiator is as conjugate of conjugate, peroxide and the sodium ascorbate of persulfate and sodium sulfite etc.; The preferred azo initiator that uses.The monomer mixture of per 100 weight portions above-mentioned containing (methyl) alkyl acrylate, the amount of the polymerization initiator of use are for example about 0.005-1 weight portions.
For emulsion polymerisation, can use chain-transferring agent to control polymeric degree.The example of chain-transferring agent comprises conventional chain-transferring agent, as mercaptan (for example, dodecyl mercaptans etc.) etc.The monomer mixture of per 100 weight portions above-mentioned containing (methyl) alkyl acrylate, the amount of the chain-transferring agent of use are for example about 0.001-0.5 weight portions.For balance skin crystallized ability and low skin irritability, preferred 0.01-0.4 weight portion, especially preferred 0.01-0.04 weight portion.
For emulsifying agent, can use anion emulsifier, as sodium lauryl sulfate, ammonium lauryl sulfate, dodecylbenzene sodium sulfonate, polyoxyethylene alkyl ether sodium sulfate (as, polyoxyethylene lauryl ether sodium sulfate), polyoxyethylene alkyl ether ammonium sulfate (as, polyoxyethylene lauryl ether ammonium sulfate), polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate etc.; Nonionic emulsifier is as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether etc.Emulsifying agent can use separately or two or more are used in combination.The monomer mixture of per 100 weight portions above-mentioned containing (methyl) alkyl acrylate, the amount of the emulsifying agent of use are for example 0.2-10 weight portion, preferably approximately 0.5-5 weight portion.
Constitute the water-dispersed copolymer of medical adhesive of the present invention, in addition to the above methods, can also be by obtaining to contain the monomer mixture of (methyl) acrylate and the copolymer of silane monomer by the method beyond the emulsion polymerisation, and by emulsifying agent this copolymer is dispersed in the water and prepares.
Medical adhesive of the present invention contain can be compatible with above-mentioned water-dispersed copolymer the organic liquid composition.
By the organic liquid composition is added in water-dispersed copolymer, can be reduced in the modulus in the low strain level of adhesive, can also keep the adhesivity good to skin, can reduce when peeling off cuticular damage, also can alleviate the pain when peeling off.
It is liquid that the employed organic liquid composition of medical adhesive of the present invention requires around under the ambient temperature situations, and presents good and compatibility water-dispersed copolymer, preferably, is difficult for transferring to medical apparatus during use, medical treatment device is first-class.
In the present invention, " compatible " is meant that the organic liquid uniform component is dissolved in water-dispersed copolymer, and wherein isolating range estimation is confirmed to be impossible.
In medical adhesive of the present invention, the example of preferred organic liquid composition comprises monoacid or the polyprotic acid with 8-18 carbon atom and the ester with branched-chain alcoho of 14-18 carbon atom, and has the saturated or unsaturated fatty acid (the straight or branched unsaturated fatty acid that preferably has 14-18 carbon atom) of the straight or branched of 12-18 carbon atom and tetravalence or the ester of the alcohol of low price more.
When use is less than the monoacid of 8 carbon atoms or polyprotic acid, to be easier to transfer on medical apparatus, the armarium etc., and when using, may reduce with the compatible ability of water-dispersed copolymer, and may not obtain good adhesivity more than the monoacid of 18 carbon atoms or polyprotic acid.Therefore, preferred monoacid or the polyprotic acid that use with 8-18 carbon atom.
When use be less than 14 carbon atoms, be the branched-chain alcoho of liquid under the room temperature condition, and the carrier of medical adhesive dressing band or sheet adhesive is that plasticizer can be transferred when allowing material such as unplasticizied polrvinyl chloride that plasticizer shifts.When the branched-chain alcoho that uses more than 18 carbon atoms, may reduce compatible ability with water-dispersed copolymer.Therefore, the preferred branched-chain alcoho that uses with 14-18 carbon atom.
The example of ester that has the monoacid or the polyprotic acid of 8-18 carbon atom and have a branched-chain alcoho of 14-18 carbon atom comprises dodecylic acid isooctadecane ester, tetradecanoic acid 2-Methylpentadecane ester, tetradecanoic acid octyl group dodecane ester, hexadecanoic acid isooctadecane ester, octadecanoid acid 2-Methylpentadecane ester, oleic acid octyl group dodecane ester, adipic acid two isooctadecane esters, decanedioic acid two 2-Methylpentadecane esters, tri trimellitate oleyl ester, tri trimellitate 2-Methylpentadecane ester etc.
Straight or branched example saturated or unsaturated fatty acid with 12-18 carbon atom comprises myristoleic acid (myristoyleic acid), oleic acid, linoleic acid, linolenic acid, different Palmic acid, isostearic acid, lauric acid etc., and the example of tetravalence or alcohol more at a low price comprises ethylene glycol, propylene glycol, glycerol, trimethylolpropane, tetramethylolmethane, sorbitan etc.
Example with ester of the straight or branched of 12-18 carbon atom saturated or unsaturated fatty acid and tetravalence or alcohol more at a low price comprises three oleic acid sorbitan esters, single oleic acid sorbitan ester, mono laurate sorbitan ester etc.
The preferred above-mentioned water-dispersed copolymer of per 100 weight portions of medical adhesive of the present invention contains the 10-100 weight portion, more preferably 20-80 weight portion organic liquid composition.
Medical adhesive of the present invention can obtain by following method: the adhesive compound that will contain above-mentioned water-dispersed copolymer and above-mentioned organic liquid composition is applied to carrier, barrier liner (releaseliner) etc. and is dried.Baking temperature is general about to be 80-140 ℃, and preferably approximately 90-130 ℃, generally be about 1-10 minute drying time.By the above-mentioned drying of heat treated, can carry out crosslinked by silane monomer.The dried thickness of medical adhesive of the present invention generally is about 10-150 μ m, preferably approximately 30-70 μ m.
When adhesive compound is applied to carrier or barrier liner, can use thickening agent as required to help applying.The example of thickening agent comprises Primal ASE-60 (ROHM AND HAASJAPAN KK. manufacturing), ARON B-500 (TOAGOSEI CO., LTD makes) etc.
In first medical adhesive of the present invention, preferably form adhesive by in water-dispersed copolymer, adding the organic liquid composition with the insoluble content of 30-80wt%.In other words, in first medical adhesive of the present invention, the gel percentage rate of crosslinked back water-dispersed copolymer preferably is adjusted to 30-80wt%.
As mentioned above, because medical adhesive of the present invention has used by the crosslinked water-dispersed copolymer of silane monomer, therefore can improve the cohesive force of adhesive and can present suitable adhesive tension.
In the present invention, the gel percentage rate of water-dispersed copolymer " crosslinked back " refers to the gel percentage rate by water-dispersed copolymer in the crosslinked adhesive of silane monomer.
Herein, in the present invention, the gel percentage rate of water-dispersed copolymer is the value by following method measurements and calculations.
(the percentile measuring method of gel)
Get about 0.04g adhesive (sample), (W accurately weighs
1).Sample immersed under the ambient temperature conditions in the ethyl acetate 7 days around, extracted the solvable content of solvent.Poly tetrafluoroethylene by average pore size 0.2 μ m (for example, the TEMISH that NITTO DENKO CORPORATION makes) filters out residue (insoluble content), and 130 ℃ of dryings 1 hour, (W weighed
2), determine insoluble content (wt%) by following formula.
Gel percentage rate (%)=(W
2* 100)/(W
1* A/B)
The weight of A=(water-dispersed copolymer+cross-linking agent)
The weight of B=(water-dispersed copolymer+organic liquid composition+cross-linking agent).
In above-mentioned formula A and B, " cross-linking agent " refers to the cross-linking agent the silane monomer contained in adhesive.
In the present invention's first medical adhesive, the preferred 30-80wt% of gel percentage rate of crosslinked back water-dispersed copolymer, more preferably 40-70wt%.
When the gel percentage rate is less than 30wt% when (especially, being less than 40wt%), it is not enough that the cohesive force of adhesive becomes.The result is that adhesive can be retained on the skin when peeling off, and adhesive can ooze out from the side of medical adhesive dressing band or sheet adhesive.When carrier is porous carrier (as non-woven fabrics etc.), the adhesive penetrating carrier.On the other hand, when the gel percentage rate surpasses 80wt%, may not obtain competent skin adhesive strength.
In the present invention's second medical adhesive, by add can be compatible with above-mentioned water-dispersed copolymer the organic liquid composition, and undertaken crosslinkedly by silane monomer, crosslinked back gel percentage rate is adjusted to 40-80wt%, preferred 40-70wt%.
As a result, medical adhesive of the present invention is a kind of low skin irritant medical adhesive, wherein is dissolved in water-dispersed copolymer to the organic liquid uniform component.And because water-dispersed copolymer is crosslinked by silane monomer, medical adhesive of the present invention presents improved cohesive force, and can demonstrate suitable adhesive tension.
When the above-mentioned gel percentage rate of crosslinked back water-dispersed copolymer was less than 40wt%, it is not enough that the cohesive force of adhesive will become.The result is that adhesive can be retained on the skin when peeling off, and adhesive can ooze out from the side of medical adhesive dressing band or sheet adhesive.When carrier is porous carrier (as non-woven fabrics etc.), the adhesive penetrating carrier.On the other hand, when the gel percentage rate of crosslinked back water-dispersed copolymer surpasses 80wt%, may not obtain competent skin adhesive strength.
In the present invention's first medical adhesive, the weight average molecular weight of the above-mentioned colloidal sol composition of crosslinked back water-dispersed copolymer preferably is not less than 300000, more preferably is not less than 400000.
In the present invention's second medical adhesive, the weight average molecular weight of the above-mentioned colloidal sol composition of crosslinked back water-dispersed copolymer is not less than 300000, preferably is not less than 400000.When being lower than 300000, fixed performance may reduce, and may not obtain competent adhesivity.
In the present invention, " the colloidal sol composition of crosslinked back water-dispersed copolymer " refers to the colloidal sol composition of the water-dispersed copolymer in the adhesive crosslinked by silane monomer.
In medical adhesive of the present invention, the gel percentage rate of crosslinked preceding water-dispersed copolymer preferably is adjusted to no more than 30wt%, more preferably no more than 28wt%.When crosslinked preceding gel percentage rate surpasses 30wt%, pain and appearance will easily take place such as the damage of peeling off keratodermatitis when peeling off.
In the present invention, " the gel percentage rate of water-dispersed copolymer before crosslinked " refers in no crosslinked adhesive the gel percentage rate of water-dispersed copolymer.Particularly, the gel percentage rate of water-dispersed copolymer " crosslinked before " refer to except that do not use can with the silane monomer of (methyl) alkyl acrylate copolymer, in the adhesive of under the condition identical, making with medical adhesive of the present invention, the gel percentage rate of water-dispersed copolymer.
And in medical adhesive of the present invention, the weight-average molecular weight/number-average molecular weight (just, molecular weight distribution) of the colloidal sol composition of crosslinked back water-dispersed copolymer is 3-7, more preferably 3-5 preferably.When this value was lower than 3, molecular weight distribution became too little and the characteristic that can not obtain needing, and when this value surpassed 7, the content ratio of low-molecular weight copolymer increased, and may not show need characteristic.
Herein, in the present invention, the weight average molecular weight of the colloidal sol composition of water-dispersed copolymer and weight-average molecular weight/number-average molecular weight (ratio) are the values by following method measurements and calculations.
(measuring method of the molecular weight of colloidal sol composition)
Get adhesive (sample) (approximately 0.04g), sample immersed under the ambient temperature conditions in the ethyl acetate 7 days around, removed insoluble content, and the solvable content of the solvent of gained is dry and obtain the tetrahydrofuran solution that concentration is 1.0g/L.This solution via hole diameter is that the membrane filter of 0.45 μ m filters, filter liquor (100 μ l) through gel permeation chromatography (for example, analytical equipment: TOSOH HLC-8120GPC (TOSOH CORPORATION manufacturing), post: tsk gel GMH-H (S), 2, flow velocity 0.5ml/min, 40 ℃ of column temperatures, and measure retention time detector RI).With the polystyrene is the basic calculation molecular weight, calculates molecular weight and molecular weight distribution (weight-average molecular weight/number-average molecular weight) that weight average molecular weight is not less than 10000 polymer.
Can control the weight average molecular weight of gel percentage rate, colloidal sol composition and the weight-average molecular weight/number-average molecular weight of colloidal sol composition by in the preparation process of medical adhesive, selecting the amount etc. of chain-transferring agent of carboxylic monomeric amount, the use of ratio, the adding of the monomer mixture of suitable containing (methyl) alkyl acrylate and silane monomer from for example above-mentioned preferable range.
Medical adhesive dressing band of the present invention and sheet adhesive contain medical adhesive of the present invention at least on the one side of carrier.In other words, medical adhesive dressing band of the present invention and sheet adhesive have the adhesive layer that contains medical adhesive of the present invention at least on the one side of carrier.
Promptly, medical adhesive dressing band of the present invention and sheet adhesive can be made like this: directly above-mentioned adhesive compound is applied on the one or both sides of carrier, here the adhesive compound of mentioning is exactly a medical adhesive of the present invention, it contains water-dispersed copolymer and organic liquid composition, be dried, perhaps on carrier, form the adhesive layer that medical adhesive of the present invention is made by adhering to by the material of the adhesive compound acquisition on coating and the dry barrier liner on the carrier.Baking temperature generally is about 80-140 ℃, and preferably approximately 90-130 ℃, generally be about 1-10 minute drying time.By above-mentioned heating and dried, can carry out crosslinked by silane monomer.The thickness of dried adhesive layer generally is about 10-150 μ m, preferably approximately 30-70 μ m.
In addition, medical adhesive dressing band of the present invention also can be cut into band and obtain then by preparation medical adhesive dressing sheet of the present invention.
When adhesive compound will be applied to carrier or barrier liner, can add thickening agent as required to help applying.The example of thickening agent comprises Primal ASE-60 (ROHM ANDHAAS JAPAN KK. manufacturing), ARON B-500 (TOAGOSEI CO., LTD makes) etc.
Though the carrier that the present invention uses is not particularly limited, as long as it can keep medical adhesive layer of the present invention, for example, thin film, band or the sheet carrier that is used for adhering bandage, surgical tape, first aid adhesive tape, large scale adhesive tape, stretch tight bundle material, paste etc. can use.These carriers can be porous or atresias.
The thickness of carrier is not particularly limited, and suitably selects according to user demand.General about 30-300 μ m.
Thereby medical adhesive dressing band of the present invention and sheet adhesive can be carried medicine and be made percutaneous plaster or transdermal absorption formulation.Entrained medicine is not particularly limited, as long as it can be carried by adhesive of the present invention.
Embodiment
Describe the present invention below by embodiment, but it can not to be interpreted as be limitation of the present invention.
Embodiment 1
Emulsifying 2-ethylhexyl acrylate (86.5 weight portion), methyl methacrylate (9.6 weight portion), acrylic acid (3.9 weight portion), 3-methacryloxypropyl trimethoxy silane (0.05 weight portion), 1-dodecyl mercaptans (0.05 weight portion), polyoxyethylene lauryl ether sodium sulfate (3 weight portion) and water (44.2 weight portion) obtain monomer emulsions in homo-mixer.Above-mentioned monomer emulsions (5.2 weight portion) and water (56.3 weight portion) are placed reaction vessel (removable flask), and this reaction vessel has condenser, nitrogen access tube, thermometer and agitator, stirs this mixture 1 hour, feeds noble gas simultaneously.Then, adding polymerization initiator 2,2 '-azo two [N-(2-carboxyethyl)-2-methyl-prop amidine] hydrate (0.1 weight portion), mixture was 60 ℃ of reactions 1 hour.Dripped above-mentioned monomer emulsions (141.1 weight portion) in 4 hours at 60 ℃, this mixture under uniform temp further aging 3 hours adds ammonia and regulates pH to 7, obtains water-dispersed copolymer.In 100 weight parts waters-dispersed copolymer (solids content), add three oleic acid sorbitan esters (30 weight portion) as the organic liquid composition, thereby obtain adhesive.
With thickening agent (Primal ASE-60 (ROHM AND HAAS JAPAN KK. manufacturing), 0.5 weight portion) add in the adhesive (100 weight portion) of gained, to have that the adhesive that improves viscosity is applied on the barrier liner and the dried thickness that obtains 40 μ m, and 130 ℃ of dryings 3 minutes.The laminated material that obtains is sticked to (23g/m on polyester/paper slurry (pulp) blended non-woven fabrics
2), obtain sheet adhesive.
Embodiment 2
Except that the quantitative change of 3-methacryloxypropyl trimethoxy silane is that the quantitative change of 0.02 weight portion and 1-dodecyl mercaptans is 0.02 weight portion, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Embodiment 3
Except that the quantitative change of 3-methacryloxypropyl trimethoxy silane is that 0.08 weight portion and acrylic acid quantitative change are 5 weight portions, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Embodiment 4
Except that the 3-methacryloxypropyl trimethoxy silane becomes 3-acryloxy propyl trimethoxy silicane, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Embodiment 5
Except that the 3-methacryloxypropyl trimethoxy silane becomes 3-methacryloxypropyl triethoxysilane, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Embodiment 6
Except that acrylic acid quantitative change is 2 weight portions, adopt the mode identical to obtain sheet adhesive with embodiment 2.
Embodiment 7
Except that the 2-ethylhexyl acrylate becomes acrylic acid ester in the different ninth of the ten Heavenly Stems and methyl methacrylate becomes the ethyl methacrylate, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Comparative Examples 1
The quantitative change that removes three oleic acid sorbitan esters is 40 weight portions, and adding epoxy resin cross-linking agent TEPIC-S (NISSAN CHEMICAL INDUSTRIES, the LTD manufacturing) (0.2 weight portion) is as cross-linking agent, rather than add outside the 3-methacryloxypropyl trimethoxy silane, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Comparative Examples 2
The cross-linking agent that removes Comparative Examples 1 becomes epoxy resin cross-linking agent, outside the DENACOL EX-321 (Nagase Chemtex Corporation makes, 0.2 weight portion), adopts the mode identical with embodiment 1 to obtain sheet adhesive.
Comparative Examples 3
The cross-linking agent that removes Comparative Examples 1 becomes azoles quinoline cross-linking agent, EPOCROS WS-700 (NIPPON SHOKUBAT CO., LTD makes), and solids content is outside 0.2 weight portion, adopts the mode identical with embodiment 1 to obtain sheet adhesive.
Comparative Examples 4
Under inert gas atmosphere, polymerization contains the monomer mixture of 2-ethylhexyl acrylate (95 weight portion) and acrylic acid (5 weight portion) in ethyl acetate, obtains acrylate copolymer.In ethyl acetate, the solids content (100 weight portion) and three oleic acid sorbitan esters (40 weight portion) and trifunctional isocyanates (CORONATE L (trade name) of mixing acrylate copolymer, NIPPONPOLYURETHANE INDUSTRY CO., LTD makes, 0.33 weight portion) (as cross-linking agent) obtains adhesive solvent.Use this adhesive solvent, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Comparative Examples 5
Except that not adding the 3-methacryloxypropyl trimethoxy silane, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Comparative Examples 6
Except that the quantitative change of 3-methacryloxypropyl trimethoxy silane is that the quantitative change of 3 weight portions and 1-dodecyl mercaptans is 0.08 weight portion, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Comparative Examples 7
Except that not adding the acrylic acid, adopt the mode identical to obtain sheet adhesive with embodiment 1.
Embodiment 8
Emulsifying 2-ethylhexyl acrylate (86.5 weight portion), methyl methacrylate (9.6 weight portion), acrylic acid (3.9 weight portion), 3-methacryloxypropyl trimethoxy silane (0.05 weight portion), 1-dodecyl mercaptans (0.035 weight portion), polyoxyethylene lauryl ether sodium sulfate (3 weight portion) and water (44.2 weight portion) obtain monomer emulsions in homo-mixer.Above-mentioned monomer emulsions (5.2 weight portion) and water (56.3 weight portion) are placed reaction vessel (removable flask), and this reaction vessel has condenser, nitrogen access tube, thermometer and agitator, stirs this mixture 1 hour, feeds noble gas simultaneously.Then, adding polymerization initiator 2,2 '-azo two [N-(2-carboxyethyl)-2-methyl-prop amidine] hydrate (0.1 weight portion), mixture was 60 ℃ of reactions 1 hour.Dripped above-mentioned monomer emulsions (141.1 weight portion) in 4 hours at 60 ℃, this mixture under uniform temp further aging 3 hours adds ammonia and regulates pH to 7, obtains water-dispersed copolymer.In 100 weight parts waters-dispersed copolymer (solids content), add three oleic acid sorbitan esters (30 weight portion) as the organic liquid composition, thereby obtain adhesive.
With thickening agent (Primal ASE-60 (ROHM AND HAAS JAPAN KK. manufacturing), 0.5 weight portion) add in the adhesive (100 weight portion) of gained, to have that the adhesive that improves viscosity is applied on the barrier liner and the dried thickness that obtains 40 μ m, and 130 ℃ of dryings 3 minutes.The laminated material that obtains is sticked to (23g/m on polyester/paper slurry (pulp) blended non-woven fabrics
2), obtain sheet adhesive.
Embodiment 9
Except that the 3-methacryloxypropyl trimethoxy silane becomes 3-acryloxy propyl trimethoxy silicane, adopt the mode identical to obtain sheet adhesive with embodiment 8.
Embodiment 10
Except that the 3-methacryloxypropyl trimethoxy silane becomes 3-methacryloxypropyl triethoxysilane, adopt the mode identical to obtain sheet adhesive with embodiment 8.
Embodiment 11
Except that three oleic acid sorbitan esters become the mono laurate sorbitan ester, adopt the mode identical to obtain sheet adhesive with embodiment 8.
Embodiment 12
Except that three oleic acid sorbitan esters become single oleic acid sorbitan ester, adopt the mode identical to obtain sheet adhesive with embodiment 8.
Comparative Examples 8
Remove the polymerization initiator 2 of embodiment 8,2 '-azo two [N-(2-carboxyethyl)-2-methyl-prop amidine] hydrate becomes Ammonium persulfate. (0.1 weight portion), add TEPIC-S (NISSAN CHEMICALINDUSTRIES.LTD) (0.2 weight portion) as cross-linking agent, and do not use outside the 3-methacryloxypropyl trimethoxy silane, adopt the mode identical to obtain sheet adhesive with embodiment 8.
Experimental example 1
The sheet adhesive that obtains among embodiment 1-7 and the Comparative Examples 1-7 is measured following character (in each test, n=3).
Insoluble content in the adhesive (gel percentage rate)
Get the adhesive (approximately 0.04g) in each sample and the (W that accurately weighs
1).Sample immersed down in the ethyl acetate 7 days at 23 ℃, extracted the solvable content of solvent.Get insoluble content, after 1 hour, (W weighs 130 ℃ of dryings
2), insoluble content (wt%) calculates by following formula.
(W
2×100)/(W
1×A/B)
The weight of A=(water-dispersed copolymer+cross-linking agent)
The weight of B=(water-dispersed copolymer+organic liquid composition+cross-linking agent)
The adhesive strength test
The sample that is cut into the long 50mm of the wide 12mm roller by 2kg made a round trip to press to be bonded on the bakelite plate, and after 30 minutes, peel sample, peel angle are 180 °, and speed is 300mm/min, measures release force (release force) at that time.
Fixed performance test (normal condition)
The formation diameter that the sample of wide with being cut into (12mm), long (55mm) will be curved is that the vinyl chloride pipe (interior diameter 3mm, overall diameter 5mm, long 70mm) of the circular arc of 20mm is fixed on experimenter's the arm.After past 6 hours, the naked-eye observation ickiness.During observation, the sample of not peeling off fully and in covering the part of center of arc, discharge but pipe fixed and stop thereon and the identified as samples of not extruding from the two ends of sample is designated as zero, all the other are labeled as *.
Fixed performance test (absorption of perspiration)
Testing under the condition identical in (normal condition), each sample is fixed on experimenter's the arm with fixed performance.The experimenter after treating 1 hour under the 45 ℃/95%R.H. condition, the naked-eye observation ickiness.During observation, the sample of not peeling off fully and in covering the part of center of arc, discharge but pipe fixed and stop thereon and the identified as samples of not extruding from the two ends of sample is designated as zero, all the other are labeled as *.
Skin irritation
The basis of test is a sample after pasting 6 hours, the pain during from experimenter's back peel sample.When peeling off, do not have pain or slight sensation is arranged but when painful, be labeled as zero, when pain, be labeled as *.
Table 1
| Gel percentage rate (%) | Bonding strength (N/12mm) | Fixed performance (normal condition) | Fixed performance (absorption of perspiration) | Skin irritation | |
| Embodiment 1 | 51 | 1.6 | ○ | ○ | ○ |
| Embodiment 2 | 52 | 1.9 | ○ | ○ | ○ |
| Embodiment 3 | 48 | 1.6 | ○ | ○ | ○ |
| Embodiment 4 | 41 | 2.2 | ○ | ○ | ○ |
| Embodiment 5 | 55 | 1.9 | ○ | ○ | ○ |
| Embodiment 6 | 50 | 1.1 | ○ | ○ | ○ |
| Embodiment 7 | 53 | 1.5 | ○ | ○ | ○ |
| Comparative Examples 1 | 48 | 1.7 | × | × | ○ |
| Comparative Examples 2 | 43 | 2.6 | × | × | ○ |
| Comparative Examples 3 | 43 | 2.3 | × | × | ○ |
| Comparative Examples 4 | 64 | 1.1 | ○ | × | ○ |
| Comparative Examples 5 | 28 | 4.0 | × | × | × |
| Comparative Examples 6 | 77 | 0.6 | × | × | ○ |
| Comparative Examples 7 | 32 | 3.2 | × | × | × |
Result by last table 1 can be clear that medical adhesive of the present invention and medical adhesive dressing sheet have good fixed performance (normal condition and absorption of perspiration), cause low skin irritation, and have competent adhesive strength.
Experimental example 2
The sheet adhesive that obtains in embodiment 8-12 and the Comparative Examples 8 is measured following character (in each test, n=3).
The insoluble content (gel percentage rate) of crosslinked back adhesive
Get the adhesive (approximately 0.04g) in each sample in embodiment and the Comparative Examples and the (W that accurately weighs
1).Sample immersed under the ambient temperature conditions in the ethyl acetate 7 days around, extracted the solvable content of solvent.By poly tetrafluoroethylene (average pore size 0.2 μ m, NITTO DENKOCORPORATION make, TEMISH) filtration residue (insoluble content), 130 ℃ of dryings 1 hour, (W weighed
2), insoluble content (wt%) calculates by following formula.
(W
2×100)/(W
1×A/B)
The weight of A=(water-dispersed copolymer+cross-linking agent)
The weight of B=(water-dispersed copolymer+organic liquid composition+cross-linking agent)
The insoluble content (gel percentage rate) of the crosslinked preceding adhesive of embodiment 8-12
Except that not using 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane or 3-methacryloxypropyl triethoxysilane, adopt the mode identical to obtain sheet adhesive with embodiment 8-12.Calculate the gel percentage rate of the adhesive in the sheet adhesive of gained according to the measurement result of the insoluble content of crosslinked back adhesive.The result is that the gel percentage rate is 26%.This gel percentage rate is considered to the crosslinked preceding gel percentage rate of embodiment 8-12.
The insoluble content (gel percentage rate) of the crosslinked preceding adhesive of embodiment 8
Except that not using the TEPIC-S, adopt the mode identical to obtain sheet adhesive with Comparative Examples 8.Calculate the gel percentage rate of the adhesive in the sheet adhesive of gained according to the measurement result of the insoluble content of crosslinked back adhesive.The result is that the gel percentage rate is 50%.This gel percentage rate is considered to the gel percentage rate of Comparative Examples.
The measurement of colloidal sol component molecules amount
The extract (solvable content) that the desiccant gel percentage rate obtains in measuring and to obtain concentration be the tetrahydrofuran solution of 1.0g/L.This solution via hole diameter is that the membrane filter of 0.45 μ m filters, filter liquor (100 μ l) is through gel permeation chromatography (analytical equipment: TOSOH HLC-8120GPC (TOSOHCORPORATION manufacturing), post: tsk gel GMH-H (s), 2, flow velocity 0.5ml/min, 40 ℃ of column temperatures, detector RI), measure retention time.With the polystyrene is the basic calculation molecular weight, calculates molecular weight and molecular weight distribution (weight-average molecular weight/number-average molecular weight) that weight average molecular weight is not less than 10000 polymer.
The adhesive strength test
Adopt the mode identical to measure with experimental example 1.
Fixed performance test (normal condition)
Adopt the mode measurements and calculations identical with experimental example 1.
Fixed performance test (absorption of perspiration)
Adopt the mode measurements and calculations identical with experimental example 1.
Skin irritation
Adopt the mode measurements and calculations identical with experimental example 1.
Table 2
| Gel percentage rate (%) before crosslinked | Crosslinked back gel percentage rate (%) | Colloidal sol component molecules amount | Weight-average molecular weight/number-average molecular weight | Adhesive strength (N/12 mm) | Fixed performance (normal condition) | Fixed performance (absorption of perspiration) | Skin irritation | |
| Embodiment 8 | 26 | 51 | 499000 | 4.0 | 1.6 | ○ | ○ | ○ |
| Embodiment 9 | 26 | 41 | 550000 | 4.3 | 1.6 | ○ | ○ | ○ |
| Embodiment 10 | 26 | 55 | 460000 | 4.0 | 1.7 | ○ | ○ | ○ |
| Embodiment 11 | 26 | 54 | 499000 | 4.0 | 1.4 | ○ | ○ | ○ |
| Embodiment 12 | 26 | 50 | 499000 | 4.0 | 1.4 | ○ | ○ | ○ |
| Comparative Examples 8 | 50 | 61 | 286000 | 3.8 | 1.3 | × | × | ○ |
Result by last table 2 can be clear that medical adhesive of the present invention and medical adhesive dressing sheet have good fixed performance (normal condition and absorption of perspiration), cause low skin irritation, and have competent adhesive strength.
The application is with the patent application 2006-144150 in Japanese publication, and 2006-276941 and 2006-298209 are the basis, and the full content of these documents is hereby incorporated by.
Claims (9)
1, a kind of medical adhesive, it comprises
Water-dispersed copolymer, this water-dispersed copolymer contain the monomer mixture of (methyl) alkyl acrylate by copolymer-1 00 weight portion and the 0.005-2 weight portion can obtain with the silane monomer of (methyl) alkyl acrylate copolymer and
Organic liquid composition that can be compatible with water-dispersed copolymer.
2, the medical adhesive of claim 1, wherein, contain in the monomer mixture of (methyl) alkyl acrylate at 100 weight portions, the monomer mixture that contains (methyl) alkyl acrylate comprise the 0.1-10 weight portion can with the carboxylic monomer of (methyl) alkyl acrylate copolymer.
3, claim 1 or 2 medical adhesive, the gel percentage rate of wherein crosslinked back water-dispersed copolymer is 30-80wt%.
4, a kind of medical adhesive dressing band or sheet adhesive contain the medical adhesive of claim 1 on the one side at least of carrier.
5, a kind of medical adhesive, it comprises
Water-dispersed copolymer, this water-dispersed copolymer contain the monomer mixture of (methyl) alkyl acrylate by copolymerization and can obtain with the silane monomer of (methyl) alkyl acrylate copolymer and
Organic liquid composition that can be compatible with water-dispersed copolymer,
The gel percentage rate of wherein crosslinked back water-dispersed copolymer is 40-80wt%, and the weight average molecular weight of the colloidal sol composition of crosslinked back water-dispersed copolymer is not less than 300000.
6, the medical adhesive of claim 5, the no more than 30wt% of gel percentage rate of wherein crosslinked preceding water-dispersed copolymer.
7, the medical adhesive of claim 5, the weight-average molecular weight/number-average molecular weight of the colloidal sol composition of wherein crosslinked back water-dispersed copolymer is 3-7.
8, the medical adhesive of claim 5, wherein, contain in the monomer mixture of (methyl) alkyl acrylate at 100 weight portions, the monomer mixture that contains (methyl) alkyl acrylate comprise the 0.1-10 weight portion can with the carboxylic monomer of (methyl) alkyl acrylate copolymer, and water-dispersed copolymer obtains by the monomer mixture that copolymerization 0.005-2 weight portion can contain (methyl) alkyl acrylate with the silane monomer and 100 weight portions of (methyl) alkyl acrylate copolymer.
9, a kind of medical adhesive dressing band or sheet adhesive contain the medical adhesive of claim 5 on the one side at least of carrier.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006-144150 | 2006-05-24 | ||
| JP2006144150 | 2006-05-24 | ||
| JP2006144150 | 2006-05-24 | ||
| JP2006276941 | 2006-10-10 | ||
| JP2006-276941 | 2006-10-10 | ||
| JP2006276941A JP4970888B2 (en) | 2006-05-24 | 2006-10-10 | Medical adhesive and medical adhesive tape or sheet |
| JP2006298209A JP4988306B2 (en) | 2006-11-01 | 2006-11-01 | Medical adhesive and medical adhesive tape or sheet |
| JP2006-298209 | 2006-11-01 | ||
| JP2006298209 | 2006-11-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101077422A true CN101077422A (en) | 2007-11-28 |
| CN101077422B CN101077422B (en) | 2013-03-27 |
Family
ID=38578482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101097235A Active CN101077422B (en) | 2006-05-24 | 2007-05-24 | Medical adhesive and medical adhesive tape or sheet |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US7897683B2 (en) |
| EP (1) | EP1867347B1 (en) |
| CN (1) | CN101077422B (en) |
| AT (1) | ATE513566T1 (en) |
| CA (1) | CA2590030C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711889A (en) * | 2008-09-30 | 2010-05-26 | 日东电工株式会社 | Pressure-sensitive adhesive tape or sheet for application to skin, and process for producing the same |
| CN102885672A (en) * | 2011-07-21 | 2013-01-23 | 日东电工株式会社 | Production method for medical pressure-sensitive adhesive tape or sheet |
| CN104479598A (en) * | 2014-11-27 | 2015-04-01 | 苏州市贝克生物科技有限公司 | Waterproof medical adhesive and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5665116B2 (en) * | 2009-11-20 | 2015-02-04 | 日東電工株式会社 | Patches and patch preparations |
| JP5652867B2 (en) * | 2009-11-20 | 2015-01-14 | 日東電工株式会社 | Medical adhesive composition |
| CN104449414B (en) * | 2014-11-25 | 2016-08-24 | 武汉君安友联医疗科技有限责任公司 | A kind of ester acrylate pressure-sensitive glue for medical use and preparation method thereof |
| CN106681488A (en) * | 2015-07-20 | 2017-05-17 | 谢培树 | Digital eyewear operated by head |
| US11661533B2 (en) * | 2017-07-28 | 2023-05-30 | Avery Dennison Corporation | Pressure sensitive adhesives and articles with hyperbranched silsesquioxane core and methods of making the same |
| EP3878482A1 (en) | 2020-03-11 | 2021-09-15 | Nitto Belgium NV | Electrically switchable adhesives for application on skin and related products and uses |
| CN113908326A (en) * | 2021-09-22 | 2022-01-11 | 华南理工大学 | Medical adhesive for repairing skin wound and using method thereof |
| CN113925996A (en) * | 2021-09-22 | 2022-01-14 | 华南理工大学 | Medical adhesive for bone defect repair and using method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4716194A (en) | 1985-11-25 | 1987-12-29 | National Starch And Chemical Corporation | Removable pressure sensitive adhesive |
| JP3014188B2 (en) | 1991-09-09 | 2000-02-28 | 日東電工株式会社 | Acrylic gel material and acrylic gel preparation |
| JP2539330B2 (en) | 1993-05-11 | 1996-10-02 | 日東電工株式会社 | Medical adhesive and medical external material formed using the same |
| JP4803916B2 (en) * | 2001-07-27 | 2011-10-26 | 日東電工株式会社 | Acrylic pressure-sensitive adhesive and method for producing the same |
| CN1263818C (en) * | 2003-06-09 | 2006-07-12 | 日东电工株式会社 | Water dispersible adhesive composition, adhesive sheet and rubber foam adhesive sheet employing the same |
| US7008987B2 (en) * | 2003-06-10 | 2006-03-07 | Nitto Denko Corporation | Aqueous dispersion type pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and pressure-sensitive adhesive rubber foam sheet using the sheet |
-
2007
- 2007-05-21 US US11/802,190 patent/US7897683B2/en active Active
- 2007-05-23 CA CA2590030A patent/CA2590030C/en not_active Expired - Fee Related
- 2007-05-23 EP EP20070252122 patent/EP1867347B1/en active Active
- 2007-05-23 AT AT07252122T patent/ATE513566T1/en active
- 2007-05-24 CN CN2007101097235A patent/CN101077422B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711889A (en) * | 2008-09-30 | 2010-05-26 | 日东电工株式会社 | Pressure-sensitive adhesive tape or sheet for application to skin, and process for producing the same |
| CN102885672A (en) * | 2011-07-21 | 2013-01-23 | 日东电工株式会社 | Production method for medical pressure-sensitive adhesive tape or sheet |
| CN104479598A (en) * | 2014-11-27 | 2015-04-01 | 苏州市贝克生物科技有限公司 | Waterproof medical adhesive and preparation method thereof |
| CN104479598B (en) * | 2014-11-27 | 2016-10-19 | 苏州市贝克生物科技有限公司 | Water proofing property medical adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070275239A1 (en) | 2007-11-29 |
| ATE513566T1 (en) | 2011-07-15 |
| CA2590030C (en) | 2015-02-10 |
| CN101077422B (en) | 2013-03-27 |
| EP1867347B1 (en) | 2011-06-22 |
| EP1867347A1 (en) | 2007-12-19 |
| CA2590030A1 (en) | 2007-11-24 |
| US7897683B2 (en) | 2011-03-01 |
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